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US4145330A - Flame retardant polypivalolactone compositions - Google Patents

Flame retardant polypivalolactone compositions Download PDF

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Publication number
US4145330A
US4145330A US05/851,051 US85105177A US4145330A US 4145330 A US4145330 A US 4145330A US 85105177 A US85105177 A US 85105177A US 4145330 A US4145330 A US 4145330A
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sup
composition
polypivalolactone
amount
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US05/851,051
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Paul A. Zorzi
Thomas S. Allen
Michael E. Kucsma
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Albemarle Corp
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Ethyl Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • This invention relates to polypivalolactone resin compositions resistant to burning. More particularly, this invention relates to the use in polypivalolactone resins of particular flame retardants which render the resin compositions resistant to burning without causing substantial deterioration in their physical properties.
  • Polypivalolactone is a well known thermoplastic material. Methods for its synthesis are described for example in U.S. Pat. Nos. 3,268,486, 3,471,456, 3,669,940 and 3,773,726, which patents are incorporated herein by reference. Applications for polypivalolactone include its use in making films (e.g., U.S. Pat. No. 3,476,714) and synthetic fiber (e.g., U.S. Pat. No. 3,299,171). Mayne, in an article entitled "The Polymerization of Pivalolactone” published in Chemtech (December, 1972), points out the usefulness of polypivalolactone as an engineering thermoplastic because of its high heat resistance.
  • polypivalolactone and most polypivalolactone compositions are their amenability to burning.
  • the polymer be rendered resistant to burning.
  • it should be rendered self-extinguishing, i.e., it should have an Underwriters Laboratory (UL) rating of at least 94VE-2.
  • UL Underwriters Laboratory
  • the flame retardant-polymer composition must not only resist burning as measured according to a specifically outlined procedure, but it should also not sustain any substantial depreciation in its important physical properties, such as tensile strength, impact strength, and color.
  • thermoplastic compositions which comprise polypivalolactone resin containing an inorganic ammonium polyphosphate in an amount up to about 45 phr sufficient to render the composition flame resistant.
  • the compositions of this invention may contain suitable quantities of various other ingredients, such as for example reinforcing fillers, plasticizers, antioxidants, thermal stabilizers, mold lubricants, auxiliary flame retardants and synergists, flow improvers, impact modifiers, and various other similar components.
  • compositions of this invention are those wherein the thermoplastic polypivalolactone resin has a limiting viscosity number in the range of from about 0.8 to about 2.5, wherein the composition contains a reinforcing amount of glass fiber reinforcing agent, and wherein the amount of the ammonium polyphosphate is up to about 30 phr. Desirable compositions additionally contain from about 1 phr to about 20 phr of a polybrominated aromatic compound.
  • the polypivalolactone will normally have a limiting viscosity number of from about 0.8 to about 3.0, a range of from about 1.5 to about 2.5 being preferred.
  • a limiting viscosity number of from about 0.8 to about 3.0, a range of from about 1.5 to about 2.5 being preferred.
  • pp. 79-81--LVN is a measure of polymer molecular weight. It will be understood that the polypivalolactone may be used as essentially the sole resinous ingredient of the composition or it may be used in the form of blends with other thermoplastics.
  • Ammonium polyphosphate flame retardants are known polymeric compounds discussion of which may be found in Kuryla and Papa, Flame Retardancy of Polymeric Materials, Vol. I (Marcel Denker, Inc., 1973), pp. 140-145.
  • the structure of ammonium polyphosphate is ##STR1## where n is greater than 50 and may run as high as 20,000. These compounds usually contain about 32% by weight of phosphorus and are known to have flame retardant properties when utilized with wood H. W. Eickner and E. L. Schaffer, Fire Technol., 3, 90 (1967)! and with rigid polyurethane foams C. E. Miles and J. W. Lyons, J. Cell. Plastics, 3, 539)1967!.
  • the amount of ammonium polyphosphate used in the compositions of the present invention may be varied and normally will involve consideration of such factors as whether or not other flame retardants are incorporated into the composition, whether or not a reinforcing filler is used, and the degree of flame resistancy desired. Usually, the amount used will fall in the range of from about 8 phr to about 45 phr. In compositions filled for example with 40-50 phr of fiberglass filler, a preferred range of proportions for the ammonium polyphosphate is between about 10 and 25 phr. In unfilled compositions a range of from about 25 phr to about 35 phr of ammonium polyphosphate generally yields a desirable, cost-efficient flame resistant material.
  • the manner of incorporating the ammonium polyphosphate into the polypivalolactone resin may be any of the conventional procedures known for adding finely particulated inorganic compounds to polymers such as Henschel mixing, roll milling, Banbury mixing, extrusion and the like.
  • Reinforcing fillers may also be incorporated into the flame resistant composition in order to enhance certain properties of the thermoplastic material. These reinforcing fillers may be used for example to obtain the degree of strength and resistance to deformation at elevated temperatures necessary for the more demanding engineering thermoplastic applications. Fillers which may be used include the so-called fiber fillers (e.g., fiberglass) and the so-called particulate fillers (e.g., alumina, silica, mullite and graphite).
  • fiber fillers e.g., fiberglass
  • particulate fillers e.g., alumina, silica, mullite and graphite
  • the amount of reinforcing filler incorporated in the flame resistant composition is largely dependent upon the characteristics desired in the composition. Generally, the amount of reinforcing filler will range from about 10 phr to about 60 phr based on the weight of the polypivalolactone resin. Preferably, the reinforcing filler ranges from about 30 phr to about 50 phr, based on the weight of the polypivalolactone resin.
  • flame retardant materials may be incorporated into the compositions of the present invention.
  • the incorporation of certain polybrominated aromatic compounds into these compositions is particularly desirable. Although a variety of compounds may be employed, polybrominated compounds are preferred.
  • Exemplary materials include pentabromotoluene; tetrabromophthalic anhydride; tetrabromophthalic acid; 3,5,3',5'-tetrabromobiphenyl ether; 2,2',4,4',6,6'-hexabromobiphenyl; 2,2-bis(3,3',5,5'-tetrabromo-4,4'-dihydroxyphenyl)propane; and bis(pentabromophenoxy)butane.
  • Preferred polybrominated aromatics are those of the formulas: ##STR2## wherein n is 2-4, most preferably 4, and each R is alike or different and selected from lower hydrocarbyl groups and halo-substituted lower hydrocarbyl groups.
  • An exemplary compound of the latter formula is bis(dimethoxyphosphinyl)tetrabromo-p-xylene.
  • the amount of polybrominated aromatic flame retardant may range from about 1 phr to about 20 phr depending on the amount of ammonium polyphosphate flame retardant utilized. More preferably, the range of the amount of polybrominated aromatic flame retardant is from about 1 phr to about 10 phr.
  • Another facet of this invention involves the use of certain metal compounds to enhance the effectiveness of the flame retardant(s) employed in the plastic compositions.
  • metal compounds include inorganic salts and oxides of antimony, arsenic, bismuth, molybdenum, tin, tungsten, zinc, etc.
  • Illustrative examples of these enhancing agents include Sb 2 O 3 , SbCl 3 , SbOCl, SbCl 5 , NaSbO 3 , As 2 O 3 , As 2 O 5 , Bi 2 O 3 , MoO 3 , SnO 2 , WO 3 , Zn(BO 2 ) 2 , Zn 3 (BO 3 ) 2 , and the like.
  • a preferred material of this type is antimony trioxide.
  • the above enhancing agents or synergists are employed in amounts sufficient to enhance the effectiveness of the ammonium polyphosphate or of the combinations of the ammonium polyphosphate and polybrominated aromatic compounds used in the polypivalolactone compositions of the invention.
  • the amount employed is from about 1 phr to about 30 phr, preferably from about 5 phr to about 15 phr.
  • Compositions of the present invention may also contain a non-dripping additive in order to reduce dripping of polymer compositions when exposed to elevated temperatures.
  • a non-dripping additive include titanium dioxide, calcium carbonate, calcium hydroxide, mica, asbestos, fiberglass, and fumed silica.
  • the amount of non-dripping additive may vary widely but will generally fall between about 1 phr and about 30 phr with the range of from about 5 phr to about 15 phr being particularly preferred.
  • nucleating agent in the compositions of the present invention to provide maximum toughness.
  • materials known to be effective as nucleating agents for other crystalline polymers can be used, such as metal salts of aromatic or alicyclic carboxylic or sulfonic acids (e.g., lithium benzoate, sodium ⁇ -naphthalene sulfonate, sodium cyclohexane carboxylate); salts of aliphatic mono or dibasic carboxylic or sulfonic acids (e.g., sodium caproate, sodium succinate); salts of arylalkyl carboxylic or sulfonic acids (e.g., aluminum phenylacetate); or particulate inorganic materials (e.g., clays, silica, titanium dioxide, and the like).
  • metal salts of aromatic or alicyclic carboxylic or sulfonic acids e.g., lithium benzoate, sodium ⁇ -naphthalene sulfonate, sodium cyclohexan
  • the amount of nucleating agent can range from about 0.01 to about 10 phr. More preferably the nucleating agent ranges from about 0.05 phr to about 2 phr.
  • antioxidants the function of which is to prevent normal oxidation
  • suitable antioxidants are 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and N-phenyl- ⁇ -napthylamine.
  • Other desirable ingredients include a coupling agent to enhance the attraction between the filler and the pivalolactone polymer, and a pigmenting material (e.g., titanium dioxide) to color the polymer composition.
  • illustrative ingredients include lubricants, other resins, light stabilizers, plasticizers, impact modifiers, etc. These various ingredients or additives may be incorporated into the resin compositions of this invention by intimately blending by either dry blending or melt blending, blending in extruders, heated rolls or other types of mixtures.
  • Nozzle Size 0.180 inches
  • test specimens so prepared were subjected to various standard test procedures in order to determine their flammability and physical or mechanical properties. Flammability testing involved subjecting as is well known, compression molded plaques to the UL-94 Vertical Burn Test. This is a specifically outlined method established by Underwriters' Laboratories whereby the flammability of a material may be established. The flammability characteristics of the material are determined in relation to specified test criteria and a rating applied. The highest rating is 94VE-0. For a material to be classified 94VE-0 it must meet three criteria.
  • VE-1 or VE-2 Materials that resist burning but do not meet the standards required by the VE-0 flame test may be classified VE-1 or VE-2 depending on their burn times, VE-2 being the lowest rating.
  • VE-2 being the lowest rating.
  • the term "flame resistant" is intended to include compositions with a VE-0, VE-1, or a VE-2 rating. The procedure for testing the specimens is outlined in Underwriters' Laboratories "The Standard for Tests for Flammability of Plastic Materials for Parts in Devices and Appliances", subject 94, September 1973, pp. 6-10, which is incorporated herein by reference.
  • Tables I and II contain formulations which exemplify the present invention. Examples 1, 2 and 3 are formulations of particularly desirable compositions and their properties. Table II contains other formulations which are illustrative of the practice of the present invention.
  • Table III shows the relative effectiveness of certain non-dripping additives when used in unreinforced polypivalolactone. The test was run in accordance with the UL-94 Vertical Burn Test described above. A value corresponding to the number of seconds that the unreinforced polymer burned before it began to drip is given for each additive at a certain usage level. The longer the polymer burned before dripping occurred, the more effective the particular additive in preventing dripping.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Flame retardant thermoplastic compositions containing polypivalolactone resin, an inorganic phosphate, and optionally a fiberglass filler and a polybrominated aromatic compound.

Description

BACKGROUND
This invention relates to polypivalolactone resin compositions resistant to burning. More particularly, this invention relates to the use in polypivalolactone resins of particular flame retardants which render the resin compositions resistant to burning without causing substantial deterioration in their physical properties.
Polypivalolactone is a well known thermoplastic material. Methods for its synthesis are described for example in U.S. Pat. Nos. 3,268,486, 3,471,456, 3,669,940 and 3,773,726, which patents are incorporated herein by reference. Applications for polypivalolactone include its use in making films (e.g., U.S. Pat. No. 3,476,714) and synthetic fiber (e.g., U.S. Pat. No. 3,299,171). Mayne, in an article entitled "The Polymerization of Pivalolactone" published in Chemtech (December, 1972), points out the usefulness of polypivalolactone as an engineering thermoplastic because of its high heat resistance.
One drawback of polypivalolactone and most polypivalolactone compositions, whether filled or unfilled, is their amenability to burning. For applications such as those mentioned above it is desirable that the polymer be rendered resistant to burning. Preferably it should be rendered self-extinguishing, i.e., it should have an Underwriters Laboratory (UL) rating of at least 94VE-2.
Finding effective flame retardants for particular polymers has proved to be no simple task. The flame retardant-polymer composition must not only resist burning as measured according to a specifically outlined procedure, but it should also not sustain any substantial depreciation in its important physical properties, such as tensile strength, impact strength, and color.
THE INVENTION
In accordance with this invention, flame retarded polypivalolactone compositions are provided in which there is no significant impairment of physical properties, such as tensile strength, impact strength and color. More particularly, this invention provides thermoplastic compositions which comprise polypivalolactone resin containing an inorganic ammonium polyphosphate in an amount up to about 45 phr sufficient to render the composition flame resistant. If desired, the compositions of this invention may contain suitable quantities of various other ingredients, such as for example reinforcing fillers, plasticizers, antioxidants, thermal stabilizers, mold lubricants, auxiliary flame retardants and synergists, flow improvers, impact modifiers, and various other similar components.
Among the preferred compositions of this invention are those wherein the thermoplastic polypivalolactone resin has a limiting viscosity number in the range of from about 0.8 to about 2.5, wherein the composition contains a reinforcing amount of glass fiber reinforcing agent, and wherein the amount of the ammonium polyphosphate is up to about 30 phr. Desirable compositions additionally contain from about 1 phr to about 20 phr of a polybrominated aromatic compound.
For use in molding operations, the polypivalolactone will normally have a limiting viscosity number of from about 0.8 to about 3.0, a range of from about 1.5 to about 2.5 being preferred. As is well known in the art--see Billmeyer, Textbook of Polymer Science, Interscience, New York, 1965, pp. 79-81--LVN is a measure of polymer molecular weight. It will be understood that the polypivalolactone may be used as essentially the sole resinous ingredient of the composition or it may be used in the form of blends with other thermoplastics.
Ammonium polyphosphate flame retardants are known polymeric compounds discussion of which may be found in Kuryla and Papa, Flame Retardancy of Polymeric Materials, Vol. I (Marcel Denker, Inc., 1973), pp. 140-145. The structure of ammonium polyphosphate is ##STR1## where n is greater than 50 and may run as high as 20,000. These compounds usually contain about 32% by weight of phosphorus and are known to have flame retardant properties when utilized with wood H. W. Eickner and E. L. Schaffer, Fire Technol., 3, 90 (1967)! and with rigid polyurethane foams C. E. Miles and J. W. Lyons, J. Cell. Plastics, 3, 539)1967!.
The amount of ammonium polyphosphate used in the compositions of the present invention may be varied and normally will involve consideration of such factors as whether or not other flame retardants are incorporated into the composition, whether or not a reinforcing filler is used, and the degree of flame resistancy desired. Usually, the amount used will fall in the range of from about 8 phr to about 45 phr. In compositions filled for example with 40-50 phr of fiberglass filler, a preferred range of proportions for the ammonium polyphosphate is between about 10 and 25 phr. In unfilled compositions a range of from about 25 phr to about 35 phr of ammonium polyphosphate generally yields a desirable, cost-efficient flame resistant material.
The manner of incorporating the ammonium polyphosphate into the polypivalolactone resin may be any of the conventional procedures known for adding finely particulated inorganic compounds to polymers such as Henschel mixing, roll milling, Banbury mixing, extrusion and the like.
Reinforcing fillers may also be incorporated into the flame resistant composition in order to enhance certain properties of the thermoplastic material. These reinforcing fillers may be used for example to obtain the degree of strength and resistance to deformation at elevated temperatures necessary for the more demanding engineering thermoplastic applications. Fillers which may be used include the so-called fiber fillers (e.g., fiberglass) and the so-called particulate fillers (e.g., alumina, silica, mullite and graphite).
The amount of reinforcing filler incorporated in the flame resistant composition is largely dependent upon the characteristics desired in the composition. Generally, the amount of reinforcing filler will range from about 10 phr to about 60 phr based on the weight of the polypivalolactone resin. Preferably, the reinforcing filler ranges from about 30 phr to about 50 phr, based on the weight of the polypivalolactone resin.
In addition to ammonium polyphosphate, other flame retardant materials may be incorporated into the compositions of the present invention. The incorporation of certain polybrominated aromatic compounds into these compositions is particularly desirable. Although a variety of compounds may be employed, polybrominated compounds are preferred. Exemplary materials include pentabromotoluene; tetrabromophthalic anhydride; tetrabromophthalic acid; 3,5,3',5'-tetrabromobiphenyl ether; 2,2',4,4',6,6'-hexabromobiphenyl; 2,2-bis(3,3',5,5'-tetrabromo-4,4'-dihydroxyphenyl)propane; and bis(pentabromophenoxy)butane. Preferred polybrominated aromatics are those of the formulas: ##STR2## wherein n is 2-4, most preferably 4, and each R is alike or different and selected from lower hydrocarbyl groups and halo-substituted lower hydrocarbyl groups. An exemplary compound of the latter formula is bis(dimethoxyphosphinyl)tetrabromo-p-xylene.
The amount of polybrominated aromatic flame retardant may range from about 1 phr to about 20 phr depending on the amount of ammonium polyphosphate flame retardant utilized. More preferably, the range of the amount of polybrominated aromatic flame retardant is from about 1 phr to about 10 phr.
Another facet of this invention involves the use of certain metal compounds to enhance the effectiveness of the flame retardant(s) employed in the plastic compositions. Such metal compounds include inorganic salts and oxides of antimony, arsenic, bismuth, molybdenum, tin, tungsten, zinc, etc. Illustrative examples of these enhancing agents include Sb2 O3, SbCl3, SbOCl, SbCl5, NaSbO3, As2 O3, As2 O5, Bi2 O3, MoO3, SnO2, WO3, Zn(BO2)2, Zn3 (BO3)2, and the like. A preferred material of this type is antimony trioxide.
The above enhancing agents or synergists are employed in amounts sufficient to enhance the effectiveness of the ammonium polyphosphate or of the combinations of the ammonium polyphosphate and polybrominated aromatic compounds used in the polypivalolactone compositions of the invention. In general, the amount employed is from about 1 phr to about 30 phr, preferably from about 5 phr to about 15 phr.
Compositions of the present invention may also contain a non-dripping additive in order to reduce dripping of polymer compositions when exposed to elevated temperatures. Among the desirable non-dripping additives are titanium dioxide, calcium carbonate, calcium hydroxide, mica, asbestos, fiberglass, and fumed silica.
The amount of non-dripping additive may vary widely but will generally fall between about 1 phr and about 30 phr with the range of from about 5 phr to about 15 phr being particularly preferred.
Although not essential, it is preferred to use a nucleating agent in the compositions of the present invention to provide maximum toughness. A variety of materials known to be effective as nucleating agents for other crystalline polymers can be used, such as metal salts of aromatic or alicyclic carboxylic or sulfonic acids (e.g., lithium benzoate, sodium α-naphthalene sulfonate, sodium cyclohexane carboxylate); salts of aliphatic mono or dibasic carboxylic or sulfonic acids (e.g., sodium caproate, sodium succinate); salts of arylalkyl carboxylic or sulfonic acids (e.g., aluminum phenylacetate); or particulate inorganic materials (e.g., clays, silica, titanium dioxide, and the like).
The amount of nucleating agent can range from about 0.01 to about 10 phr. More preferably the nucleating agent ranges from about 0.05 phr to about 2 phr.
As noted above, still other ingredients may be incorporated into the polypivalolactone formulations of this invention. Thus for example an antioxidant, the function of which is to prevent normal oxidation, may be incorporated into the flame resistant compositions. Examples of suitable antioxidants are 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and N-phenyl-β-napthylamine. Other desirable ingredients include a coupling agent to enhance the attraction between the filler and the pivalolactone polymer, and a pigmenting material (e.g., titanium dioxide) to color the polymer composition. Other illustrative ingredients include lubricants, other resins, light stabilizers, plasticizers, impact modifiers, etc. These various ingredients or additives may be incorporated into the resin compositions of this invention by intimately blending by either dry blending or melt blending, blending in extruders, heated rolls or other types of mixtures.
The following examples will serve to illustrate the invention. In Examples 1 through 22, shown in Tables I and II, blends were prepared in a Prodex-Henschel mixer and compounded either by extruding rods or by molding parts on a New Britain injection molder. The rods or parts were granulated, re-fed into the injection molder and molded into test specimens. Processing conditions are listed below:
Mixer: Prodex-Henschel, Model 2J ss
Mixing Time: 3 minutes or until temperature reached 150° F.
Mixing Speed: 1800 RPM
Molder: New Britain, Type 175
Screw Type: General purpose
Compression Ratio: 2/1
Nozzle Size: 0.180 inches
Shot Size: 1.2 inches
Temperature Profile: 430° F., 480° F., 480° F., 80% (Nozzle)
Injection Speed: Maximum
Injection Pressure: 600 psig
Back Pressure: 200 psig
Holding Time: 5 seconds
Cooling Time: 35 seconds
Mold Temperature: 165° F.
The test specimens so prepared were subjected to various standard test procedures in order to determine their flammability and physical or mechanical properties. Flammability testing involved subjecting as is well known, compression molded plaques to the UL-94 Vertical Burn Test. This is a specifically outlined method established by Underwriters' Laboratories whereby the flammability of a material may be established. The flammability characteristics of the material are determined in relation to specified test criteria and a rating applied. The highest rating is 94VE-0. For a material to be classified 94VE-0 it must meet three criteria. Of five specimens of the material tested, (1) none shall burn with flaming combustion for more than ten seconds after each application of the test flame, (2) the five specimens shall not have a total flaming combustion time exceeding 50 seconds, and (3) none of the specimens shall burn with flaming or glowing combustion up to the holding lamp. Materials that resist burning but do not meet the standards required by the VE-0 flame test may be classified VE-1 or VE-2 depending on their burn times, VE-2 being the lowest rating. The term "flame resistant" is intended to include compositions with a VE-0, VE-1, or a VE-2 rating. The procedure for testing the specimens is outlined in Underwriters' Laboratories "The Standard for Tests for Flammability of Plastic Materials for Parts in Devices and Appliances", subject 94, September 1973, pp. 6-10, which is incorporated herein by reference.
Physical and mechanical properties in the Examples summarized in Table I were determined in accordance with ASTM procedures where applicable: tensile strength--D-638; tensile elastic modulus--D-638; flexural strength--D-790; flexural elastic modulus--D-790; Izod impact--D-256; heat distortion temperature--D-648; tensile impact--D-1822. The spiral flow values were obtained by extruding the compositions at about 480° F. into a coiled spiral mold 25 inches from head to tail which is kept at about 165° F. The penetration in inches of the hot polymer composition into the cooler mold is termed the "spiral flow". Examples 4 through 22 summarized in Table II involved only flame retardancy testing.
              TABLE I                                                     
______________________________________                                    
Flame Resistance of Polypivalolactone Formulations                        
              Control                                                     
                     Ex. 1   2       3                                    
______________________________________                                    
FORMULATION (PHR)                                                         
Polypivalolactone.sup.(1)                                                 
                100      100     100   100                                
Fiberglass.sup.(2)                                                        
                43       43      43    43                                 
Coupling Agent.sup.(3)                                                    
                0.5      0.5     0.5   0.5                                
Antioxidant.sup.(4)                                                       
                0.1      0.1     0.1   0.1                                
Nucleating Agent.sup.(5)                                                  
                0.5      0.5     0.5   0.5                                
Ammonium polyphosphate.sup.(6)                                            
                --       18      10    10                                 
Decabromodiphenyl oxide                                                   
                --       --      4     --                                 
BDPTX.sup.(7)   --       --      --    5                                  
PROPERTIES                                                                
UL94 Rating     None.sup.(8)                                              
                         VE-O    VE-O  VE-O                               
Specific Gravity                                                          
                1.337    1.427   1.436 1.435                              
Tensile Strength (psi)                                                    
                8460     8320    7630  7450                               
Elongation (%)  1.30     1.33    0.97  1.10                               
Tensile Modulus 1020     1060    1140  1130                               
(×10.sup.3), (psi)                                                  
Flexural Strength (psi)                                                   
                15,200   15,000  15,000                                   
                                       13,400                             
Flexural Modulus                                                          
                946      988     1000  946                                
(×10.sup.3), (psi)                                                  
Izod Impact - 1/4"                                                        
                1.1      1.0     1.0   1.0                                
(ft - lb/in)                                                              
Izod Impact - 1/8"                                                        
                1.2      1.0     1.0   1.0                                
(ft - lb/in)                                                              
Tensile Impact  13.1     13.7    11.8  9.5                                
(ft - lb/in.sup.2)                                                        
Deflection Temp. at                                                       
                221      213     213.5 187                                
264 psi (° C.)                                                     
Deflection Temp. at                                                       
                240      229     228   226.5                              
66 psi (° C.)                                                      
Color           White    Off     Off   Off                                
                         White   White White                              
Spiral Flow (inches)                                                      
                11.5     15.5    15.5  15.5                               
______________________________________                                    
 .sup.(1) LVN 2.1; Measured in benzyl alcohol at 150° C.; Stabilize
 with 0.05 weight percent dicetyl sulfide.                                
 .sup.(2) Owens Corning Fiberglass: Grade 2219-641-3 (1/4- strands).      
 .sup.(3) A-187, glycidoxypropyltrimethoxysilane; Union Carbide           
 Corporation.                                                             
 .sup.(4)                                                                 
 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene;    
 Ethyl Corporation.                                                       
 .sup.(5) TiO.sub.2.                                                      
 .sup.(6) Phos-Chek.sup.® P/30; Monsanto Company (a flame retardant   
 containing about 32% phosphorus).                                        
 .sup.(7) Bis(dimethoxyphosphinyl)tetrabromo-p-xylene.                    
 .sup.(8) "None" indicates that the composition did not meet the          
 flammability standards required to merit a VE-0, VE-1, or a VE-2 rating. 

                                  TABLE II                                
__________________________________________________________________________
FLAME RESISTANCE OF POLYPIVALOLACTONE FORMULATIONS                        
FORMULATIONS (PHR)                                                        
              Ex. 4                                                       
                  5   6   7   8   9   10  11                              
__________________________________________________________________________
Polypivalolactone.sup.(1)                                                 
              100 100 100 100 100 100 100 100                             
Fiberglass.sup.(2)                                                        
              43  43  43  43  43  43  43  43                              
Coupling Agent.sup.(3)                                                    
              0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5                             
Antioxidant.sup.(4)                                                       
              0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1                             
Nucleating Agent.sup.(5)                                                  
              0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5                             
Ammonium Polyphosphate.sup.(6)                                            
              10  15  10  10  15  10  10  10                              
Decabromodiphenyl oxide                                                   
              10  5   5   2   --  5   --  4                               
Other         --  --  --  --  5.sup.(7)                                   
                                  --  5.sup.(9)                           
                                          --                              
UL94 Rating   VE-0                                                        
                  VE-0                                                    
                      VE-0                                                
                          VE-1                                            
                              VE-0.sup.(8)                                
                                  VE-0                                    
                                      VE-0                                
                                          VE-0                            
 .sup.(1) - .sup.(6) See Footnotes .sup.(1) - .sup.(6) under Table I.     
 .sup.(7) Tetrabromometa-xylene                                           
 .sup.(8) Volatiles observed.                                             
 .sup.(9) Bis(dimethoxyphosphinyl)tetrabromo-p-xylene.                    

FORMULATIONS (PHR)                                                        
              Ex. 12                                                      
                  13  14  15  16  17  18  19                              
__________________________________________________________________________
Polypivalolactone.sup.(1)                                                 
              100 100 100 100 100 100 100 100                             
Fiberglass.sup.(2)                                                        
              43  43  43  43  43  43  43  43                              
Coupling Agent.sup.(3)                                                    
              0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5                             
Antioxidant.sup.(4)                                                       
              0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1                             
Nucleating Agent.sup.(5)                                                  
              0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5                             
Ammonium Polyphosphate.sup.(6)                                            
              10  13  11  11  11  18  10  10                              
Decabromodiphenyl oxide                                                   
              --  2.5 3   3   3   --  4   --                              
Other         4.sup.(9)                                                   
                  --  2.sup.(10)                                          
                          2.sup.(11)                                      
                              2.sup.(12)                                  
                                  --  --  6.sup.(13)                      
UL94 Rating   VE-1                                                        
                  VE-1                                                    
                      VE-1                                                
                          VE-1                                            
                              VE-1                                        
                                  VE-0                                    
                                      VE-0                                
                                          VE-0                            
 .sup.(10) Antimony oxide (Sb.sub.2 O.sub.3).                             
 .sup.(11) Zinc borate.                                                   
 .sup.(12) Alumina hydrate.                                               
 .sup.(13) Octabromo-4,4'-dimethyldiphenylether.                          

FORMULATIONS (PHR) Ex. 20   21       22                                   
__________________________________________________________________________
Polypivalolactone.sup.(1)                                                 
                   100      100      100                                  
Fiberglass.sup.(2) 43       --       --                                   
Coupling Agent.sup.(3)                                                    
                   --       --       --                                   
Antioxidant.sup.(4)                                                       
                   0.1      0.1      0.1                                  
Nucleating Agent.sup.(5)                                                  
                   0.5      0.5      0.5                                  
Ammonium Polyphosphate.sup.(6)                                            
                   18       18       30                                   
Decabromodiphenyl oxide                                                   
                   --       --       --                                   
Other              --       --       --                                   
UL94 Rating        VE-0     None.sup.(14)                                 
                                     VE-0                                 
__________________________________________________________________________
 .sup.(14) See Footnote 8 under Table I.
Tables I and II contain formulations which exemplify the present invention. Examples 1, 2 and 3 are formulations of particularly desirable compositions and their properties. Table II contains other formulations which are illustrative of the practice of the present invention.
Table III shows the relative effectiveness of certain non-dripping additives when used in unreinforced polypivalolactone. The test was run in accordance with the UL-94 Vertical Burn Test described above. A value corresponding to the number of seconds that the unreinforced polymer burned before it began to drip is given for each additive at a certain usage level. The longer the polymer burned before dripping occurred, the more effective the particular additive in preventing dripping.
              TABLE III                                                   
______________________________________                                    
NON-DRIPPING ADDITIVES FOR UNREINFORCED                                   
POLYPIVALOLACTONE FORMULATIONS.sup.(1)                                    
              USAGE LEVEL   BURN TIME.sup.(2)                             
ADDITIVE      (phr)         (sec.)                                        
______________________________________                                    
Titanium Dioxide                                                          
              8             19                                            
Calcium Carbonate                                                         
              8             42                                            
Calcium Hydroxide                                                         
              8             62                                            
Ca Mg Aluminosilicate.sup.(3)                                             
              5             30                                            
Mica.sup.(4)  5             14                                            
Asbestos.sup.(5)                                                          
              5             55                                            
Asbestos.sup.(6)                                                          
              5             60                                            
*Asbestos.sup.(7)                                                         
              12            26                                            
Fumed Silica.sup.(8)                                                      
              2             40                                            
*Fumed Silica.sup.(9)                                                     
              5             57                                            
Fiberglass.sup.(10)                                                       
              5             28                                            
______________________________________                                    
 .sup.(1) Unless noted by an asterisk (*), the polypivalolactone          
 formulations used in this table were: Polypivalolactone--see footnote    
 .sup.(1) under Table I; Antioxidant--0.1 phr based on weight of the      
 polypivalolactone resin--see footnote .sup.(4) under Table I; Nucleating 
 Agent--0.5 phr--see footnote .sup.(5) under Table I; Ammonium            
 Polyphosphate--10 phr--see footnote .sup.(6) under Table I;              
 Decabromodiphenyl Oxide--4 phr. When marked by an asterisk (*) the       
 formulation contained 18 phr ammonium polyphosphate, no decabromodiphenyl
 oxide, and the same type and amount of polypivalolactone, antioxidant, an
 nucleating agent.                                                        
 .sup.(2) The time (in seconds) that the sample burned before dripping    
 occurred. Samples were tested in accordance with the UL-94 Vertical Burn 
 Test described above.                                                    
 .sup.(3) Calcium Magnesium Aluminosilicate; Processed Mineral Fiber, Jim 
 Walter Resources, Inc., maximum particle size 600 microns, average       
 particle size 275 microns.                                               
 .sup.(4) Suzorite 60S, a phlogopite mica produced by Marietta Resources  
 International, Ltd., maximum particle size 840 microns, average particle 
 size 200 microns.                                                        
 .sup.(5) RG-100, Union Carbide Corporation.                              
 .sup.(6) RG-600, Union Carbide Corporation.                              
 .sup.(7) Ibid.                                                           
 .sup.(8) Aerosil 200, Pegussa Company.                                   
 .sup.(9) Ibid.                                                           
 .sup.(10) Owens Corning Fiberglass; Grade 2219-641-3 1/4" Strands).

Claims (11)

What is claimed is:
1. A thermoplastic composition which comprises polypivalolactone resin and an inorganic ammonium polyphosphate present in an amount up to about 45 phr sufficient to render the composition flame resistant.
2. The composition of claim 1 including a non-dripping additive selected from the group consisting of fumed silica, asbestos and calcium hydroxide.
3. A composition of claim 1 wherein said composition also includes from 10 phr to 60 phr by weight of a reinforcing filler.
4. The composition of claim 3 wherein the amount of reinforcing filler is from about 30 phr to about 50 phr.
5. The composition of claim 3 in which the reinforcing filler is fiberglass.
6. The composition of claim 3 in which the amount of said polyphosphate is from about 10 phr to about 20 phr.
7. A composition of claim 3 which also contains from about 1 phr to about 20 phr of a polybrominated aromatic compound.
8. The composition of claim 7 wherein the polybrominated aromatic compound is decabromodiphenyl oxide.
9. The composition of claim 7 wherein the polybrominated aromatic compound is bis(dimethoxyphosphinyl)tetrabromo-p-xylene.
10. A thermoplastic composition which comprises polypivalolactone resin having a limiting viscosity number in the range of from about 0.8 to about 2.5, a reinforcing amount of glass fiber reinforcing agent, and an inorganic ammonium polyphosphate present in an amount up to about 30 phr sufficient to render the composition flame resistant.
11. A composition of claim 10 wherein said composition additionally includes from about 1 phr to about 20 phr of a polybrominated aromatic compound.
US05/851,051 1977-11-14 1977-11-14 Flame retardant polypivalolactone compositions Expired - Lifetime US4145330A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2142638A (en) * 1983-07-04 1985-01-23 Anzon Ltd Flame retardant for polymers, and polymers containing same
US5286576A (en) * 1989-08-21 1994-02-15 The B. F. Goodrich Company Compression molded flame retardant and high impact strength ultra high molecular weight polyethylene composition
KR100348750B1 (en) * 2000-07-04 2002-08-13 제일모직주식회사 Flame Retardant Thermoplastic Resin Composition
EP1502900A1 (en) * 2003-07-28 2005-02-02 Asahi Glass Company, Limited Complex flame retardant and thermoplastic resin composition containing it
US20110152391A1 (en) * 2007-09-13 2011-06-23 Wilson David R Expanded styrenic polymers containing aromatic phosphonate fr additives
CN114512723A (en) * 2017-05-22 2022-05-17 微宏动力系统（湖州）有限公司 A lithium ion secondary battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3268486A (en) * 1963-06-28 1966-08-23 Shell Oil Co Process for preparing polyesters
US3397035A (en) * 1964-12-22 1968-08-13 Monsanto Co Ammonium polyphosphates
US3669940A (en) * 1969-03-10 1972-06-13 Shell Oil Co Two-step bulk polymerization of pivalolactone
US3738959A (en) * 1972-05-22 1973-06-12 American Cyanamid Co Flame-retarded olefin polymer compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3268486A (en) * 1963-06-28 1966-08-23 Shell Oil Co Process for preparing polyesters
US3397035A (en) * 1964-12-22 1968-08-13 Monsanto Co Ammonium polyphosphates
US3669940A (en) * 1969-03-10 1972-06-13 Shell Oil Co Two-step bulk polymerization of pivalolactone
US3738959A (en) * 1972-05-22 1973-06-12 American Cyanamid Co Flame-retarded olefin polymer compositions

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2142638A (en) * 1983-07-04 1985-01-23 Anzon Ltd Flame retardant for polymers, and polymers containing same
US5286576A (en) * 1989-08-21 1994-02-15 The B. F. Goodrich Company Compression molded flame retardant and high impact strength ultra high molecular weight polyethylene composition
KR100348750B1 (en) * 2000-07-04 2002-08-13 제일모직주식회사 Flame Retardant Thermoplastic Resin Composition
EP1502900A1 (en) * 2003-07-28 2005-02-02 Asahi Glass Company, Limited Complex flame retardant and thermoplastic resin composition containing it
US20050027048A1 (en) * 2003-07-28 2005-02-03 Asahi Glass Company, Limited Complex flame retardant and thermoplastic resin composition containing it
US20110152391A1 (en) * 2007-09-13 2011-06-23 Wilson David R Expanded styrenic polymers containing aromatic phosphonate fr additives
CN114512723A (en) * 2017-05-22 2022-05-17 微宏动力系统（湖州）有限公司 A lithium ion secondary battery
CN114512723B (en) * 2017-05-22 2024-04-09 微宏动力系统（湖州）有限公司 A lithium ion secondary battery

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